CN104388841A - Anticorrosive biological magnesium-based glassy metal composite material and its preparation method - Google Patents
Anticorrosive biological magnesium-based glassy metal composite material and its preparation method Download PDFInfo
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Abstract
The invention discloses an anticorrosive biological magnesium-based glassy metal composite material and its preparation method. The alloy component atom percentage expression of the composite material is Mga(Cu0.6Ag0.2Zn0.2)b(Gd0.7Y0.3)c, a is not smaller than 70 and not greater than 85, b is not smaller than 10.8 and not greater than 21.6, c is not smaller than 4.2 and not greater than 8.4, and the value of a+b+c is 100. The preparation method comprises the following steps: uniformly smelting high melting point components in argon protection atmosphere by adopting a non-consumable arc furnace to prepare an intermediate alloy; putting the intermediate alloy and Mg and Zn elements into a crucible, and carrying out induction smelting under the protection of argon to form master alloy; putting the master alloy in a quartz glass tube, carrying out induction smelting remelting under the protection of argon, and casting through a low pressure copper die to prepare a master alloy profile; and putting the master alloy profile into a pretreated crucible, carrying out induction smelting heating under the protection of argon to completely melt, carrying out heat insulation for 10min, and carrying out rapid sequential solidification to form the metal glass composite material. The magnesium-based metal glass composite material prepared in the invention has a largest dimension reaching 16mm, and has excellent corrosion resistance and room temperature plasticity.
Description
Technical field
The invention belongs to metal-base composites technical field, particularly a kind of corrosion-resistant biological magnesium-base metal glass matrix material and preparation method thereof.
Background technology
Magnesium-base metal glass (Mg-BMG) is a kind of novel alloy of longrange disorder, there is the mechanical property that high strength, low elastic modulus etc. are unique, and the corrosion resistance nature of excellence and good biocompatibility, thus become an important development direction of Biodegradable material.But owing to lacking dislocation, the work hardening mechanism such as twin, Mg-BMG is out of shape with the shear mode of height localization, its temperature-room type plasticity extreme difference, direct brittle rupture under tensile stress.This just seriously constrains the clinical application of Mg-BMG as Biodegradable material, therefore must solve the brittleness at room temperature problem of Mg-BMG.
For improving the brittleness at room temperature of BMG material, within 2000, Johnson research group of U.S. first passage adds Nb alloy element in Zr-BMG alloy system, prepare the BMG matrix material of micron-scale β-Zr (Ti) solid solution phase plasticising, obtain good temperature-room type plasticity.Subsequently, scientific and technical personnel have developed a kind of Mg-BMG matrix material, and the room temperature compressive strain before its fracture reaches the 22%(patent No.: CN101418423).
But above-mentioned Mg-BMG matrix material Forming ability is lower, and critical size only has 6mm, is difficult to the needs meeting practical application.Therefore, a kind of Mg-BMG matrix material simultaneously with strong glass forming ability and toughness of exploitation and preparation method thereof is needed badly.
Summary of the invention
The object of the present invention is to provide a kind of Mg-BMG matrix material with strong glass forming ability and excellent toughness and preparation method thereof.
The technical solution realizing the object of the invention is: a kind of corrosion-resistant biological magnesium-base metal glass matrix material, is characterized in that the alloying constituent atomic percent expression formula of described matrix material is: Mg
a(Cu
0.6ag
0.2zn
0.2)
b(Gd
0.7y
0.3)
c, 70≤a≤85,10.8≤b≤21.6,4.2≤c≤8.4, a+b+c=100.
A kind of corrosion-resistant biological magnesium-base metal glass composite material and preparation method thereof, is characterized in that adopting rapid sequential freezing method, specifically comprises following preparation process:
The first step: be predetermined to be according to matrix material and point carry out proportioning, its alloying constituent atomic percent expression formula is: Mg
a(Cu
0.6ag
0.2zn
0.2)
b(Gd
0.7y
0.3)
c, 70≤a≤85,10.8≤b≤21.6,4.2≤c≤8.4, a+b+c=100.First under argon atmosphere, adopt non-consumable arc furnace that the high-melting-point constituent element meltings such as Cu, Ag, Gd, Y is even, be prepared into master alloy; Then master alloy is put into crucible together with Mg, Zn element, under argon shield, adopt induction melting to become mother alloy;
Second step: mother alloy is put into quartz glass tube, adopts induction melting remelting under argon shield, and makes mother alloy section bar by the casting of low pressure copper mold;
3rd step: by putting into the good crucible of pre-treatment after mother alloy section bar, under argon shield, adopts induction melting be heated to complete molten state and be incubated 10 minutes, implements rapid sequential subsequently and solidifies, form metal glass composite material.
The present invention compared with prior art, its remarkable advantage is: 1, by Composition Design and the preparation technology of science, can obtain the large size Mg-BMG matrix material of 16mm, and the volume of first separating out magnesium sosoloid phase in matrix material can adjust arbitrarily within the scope of 30-80%; 2, Mg-BMG microstructure of composite is even, and excellent in mechanical performance, also has good erosion resistance and biocompatibility.
Accompanying drawing explanation
Fig. 1 is the preparation flow figure for corrosion-resistant biological magnesium-base metal glass matrix material.
Fig. 2 is corrosion-resistant biological magnesium-base metal glass matrix material macroscopic view sample, microstructure and XRD diffractogram.
Fig. 3 is the polarization curve in the room temperature compression curve of corrosion-resistant biological magnesium-base metal glass matrix material and simulated body fluid.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail
Composition graphs 1, a kind of corrosion-resistant biological magnesium-base metal glass matrix material of the present invention, its alloying constituent atomic percent expression formula is: Mg
a(Cu
0.6ag
0.2zn
0.2)
b(Gd
0.7y
0.3)
c, 70≤a≤85,10.8≤b≤21.6,4.2≤c≤8.4, a+b+c=100.
A kind of corrosion-resistant biological magnesium-base metal glass matrix material of the present invention, its preparation method comprises the following steps:
The first step: choose purity and be greater than 99.5% alloying element, point to carry out proportioning under argon atmosphere, first adopt non-consumable arc furnace that the high-melting-point constituent element meltings such as Cu, Ag, Gd, Y is even according to being predetermined to be, be prepared into master alloy; Then master alloy is put into crucible together with Mg, Zn element, under argon shield, adopt induction melting to become mother alloy;
Second step: mother alloy is put into quartz glass tube, adopts induction melting remelting under argon shield, and makes mother alloy section bar by the casting of low pressure copper mold;
3rd step: by putting into the good crucible of pre-treatment after mother alloy section bar, under argon shield, adopts induction melting be heated to complete molten state and be incubated 10 minutes, implements rapid sequential subsequently and solidifies, form metal glass composite material.
Specific embodiment of the invention process is as follows:
(1) design of alloy:
First the alloy system (Mg-Cu-Ag-Gd) with good glass basis Forming ability is selected, and according to phase choosing principles, design the concrete alloying constituent that can form the Mg-BMG matrix material that Mg solid solution phase is separated out, add appropriate alloy element Zn and Y again, carry heavy alloyed glass forming ability further.
(2) mother alloy melting:
According to the alloying constituent that (1) obtains, under argon atmosphere, first adopt non-consumable arc furnace that the high-melting-point constituent element meltings such as Cu, Ag, Gd, Y is even, be prepared into master alloy; Then master alloy is put into crucible together with Mg, Zn element, under argon shield, adopt induction melting to become mother alloy; Again mother alloy is put into quartz glass tube, under argon shield, adopt induction melting remelting, and make mother alloy section bar by the casting of low pressure copper mold;
(3) rapid sequential solidifies
The good crucible of pre-treatment will be put into after mother alloy section bar; under argon shield; induction melting is adopted to be heated to complete molten state and to be incubated 10 minutes; immerse in the extremely strong Ga-In-Sn liquid alloy of cooling power with the withdrawing rate of 3mm/s subsequently; realize rapid sequential to solidify, form metal glass composite material.
(4) stuctures and properties characterizes
Utilize the means such as XRD, OM to carry out Microstructure characterization, mechanical property and corrosive nature to Mg-BMG matrix material to characterize, to determine to have the matrix material microtexture of best over-all properties and corresponding alloying constituent thereof and preparation technology parameter.
Below in conjunction with specific embodiment, the invention will be further described.
embodiment 1
(1) raw-materially to select
The present invention prepares the purity of each metal constituent element that master alloy ingot is selected as table 1, and alloying constituent is Mg
75(Cu
0.6ag
0.2zn
0.2)
18.3(Gd
0.7y
0.3)
6.7(atomic percent).
The purity (%) that master alloy ingot selects metal constituent element prepared by table 1
| Alloying element | Mg | Cu | Ag | Zn | Gd | Y |
| Purity/% | 99.9 | 99.9 | 99.9 | 99.9 | 99.5 | 99.5 |
(2) preparation of mother alloy section bar
First under high-purity argon gas protective condition, found master alloy buckle ingot with non-consumable arc-melting furnace, its specific procedure is as follows:
A, the surperficial mechanical grinding of refractory metal raw material Cu, Ag, Gd, Y removed surface oxide skin after, get the raw materials ready according to the composition proportion material designed; According to the weight of every ingot about 80g, the material prepared is put into the water jacketed copper crucible of smelting furnace, cover bell and be evacuated to 2 × 10
-3pa; In stove, be filled with the high-purity argon gas (99.99%) of a certain amount of pressure, argon pressure scope is 0.4 ~ 0.6MPa.
B, multi-pass melting intermediate alloy ingot: adopt non-consumable tungsten electrode that above-mentioned high-melting-point constituent element is melted 3 times together under function composite by electromagnetic stirring, obtain the master alloy button ingot mixed.The electric current adopted during melting is 500 ~ 650A, and the voltage that induction stirring adopts is 1 ~ 3V.
Second step is broken by uniform for arc melting master alloy, after mixing by design mix with low melting point constituent element Mg, Zn alloy raw material, put into pretreated plumbago crucible together, furnace chamber vacuumizes, be filled with 0.06MPa argon gas again as shielding gas, adopt induction melting to make mother alloy;
Mother alloy fragmentation is put into quartz glass tube by the 3rd step, adopts induction melting remelting under argon shield, and makes mother alloy section bar by the casting of low pressure copper mold.
(3) rapid sequential solidifies
The mother alloy section bar of above-mentioned acquisition is put into the good crucible of pre-treatment; under argon shield; induction melting is adopted to be heated to complete molten state and to be incubated 10 minutes; immerse in the extremely strong Ga-In-Sn liquid alloy of cooling power with the withdrawing rate of 3mm/s subsequently; realize rapid sequential to solidify, form metal glass composite material.
(5) stuctures and properties characterizes
The Mg-BMG composite sample of Fig. 2 (a) to be the diameter prepared by above-mentioned technique be 16mm.Fig. 2 (b) is the micro-organization chart of this sample, is uniform-distribution with the Mg solid solution phase that volume fraction is about 48% as seen on glass basis, and the casting flaw such as pore-free, shrinkage porosite in sample.Fig. 2 (c) is the XRD figure spectrum of Mg-BMG matrix material, and it further demonstrate that this matrix material is by glass basis and Mg solid solution phase two phase composite.
Fig. 3 (a) is the room temperature compressive stress strain curve of Mg-BMG matrix material prepared, and can find out that the yield strength of matrix material and plastix strain reach 750MPa and 12% respectively.Fig. 3 (b) is the electrochemical tests in simulated body fluid for Mg-BMG matrix material and traditional AZ31 magnesium alloy, the corrosion potential of this matrix material visible is about-1.25V, far above the corrosion potential of-1.63V of AZ31 magnesium alloy, show that this Mg-BMG matrix material has excellent erosion resistance.
The above-mentioned fact shows, compare existing magnesium alloy, magnesium-base metal glass and technique thereof, the Mg-BMG matrix material of the present invention's design has very strong glass forming ability, and prepare homogeneous microstructure, Mg-BMG matrix material without casting flaw, obtain excellent mechanical performances and corrosion resistance nature.
embodiment 2
Adopt the method identical with embodiment 1, alloying constituent is Mg
70(Cu
0.6ag
0.2zn
0.2)
21.6(Gd
0.7y
0.3)
8.4(atomic percent), the withdrawing rate that rapid sequential solidifies is 5mm/s.The 16mm diameter matrix material sample homogeneous microstructure of preparation, glass basis is dispersed with the Mg solid solution phase that volume fraction is about 30%.The mechanical properties of this matrix material and plastix strain reach 820MPa and 7.5% respectively, and the electrochemical corrosion potential in simulated body fluid is about-1.20V.
embodiment 3
Adopt the method identical with embodiment 1, alloying constituent is Mg
80(Cu
0.6ag
0.2zn
0.2)
14.4(Gd
0.7y
0.3)
5.6(atomic percent), the withdrawing rate that rapid sequential solidifies is 8mm/s.The matrix material sample homogeneous microstructure of preparation, glass basis is dispersed with the Mg solid solution phase that volume fraction is about 63%.The mechanical properties of this matrix material and plastix strain reach 700MPa and 14% respectively, and the electrochemical corrosion potential in simulated body fluid is about-1.32V.
embodiment 4
Adopt the method identical with embodiment 1, alloying constituent is Mg
85(Cu
0.6ag
0.2zn
0.2)
10.8(Gd
0.7y
0.3)
4.2(atomic percent), the withdrawing rate that rapid sequential solidifies is 10mm/s.The matrix material sample homogeneous microstructure of preparation, glass basis is dispersed with the Mg solid solution phase that volume fraction is about 80%.
Claims (5)
1. a corrosion-resistant biological magnesium-base metal glass matrix material, is characterized in that the alloying constituent atomic percent expression formula of described matrix material is: Mg
a(Cu
0.6ag
0.2zn
0.2)
b(Gd
0.7y
0.3)
c, 70≤a≤85,10.8≤b≤21.6,4.2≤c≤8.4, a+b+c=100.
2. a corrosion-resistant biological magnesium-base metal glass composite material and preparation method thereof, is characterized in that adopting rapid sequential freezing method, specifically comprises following preparation process:
The first step: be predetermined to be according to matrix material and point carry out proportioning, its alloying constituent atomic percent expression formula is: Mg
a(Cu
0.6ag
0.2zn
0.2)
b(Gd
0.7y
0.3)
c, 70≤a≤85,10.8≤b≤21.6,4.2≤c≤8.4, a+b+c=100; First under argon atmosphere, adopt non-consumable arc furnace that the high-melting-point constituent element meltings such as Cu, Ag, Gd, Y is even, be prepared into master alloy; Then master alloy is put into crucible together with Mg, Zn element, under argon shield, adopt induction melting to become mother alloy;
Second step: mother alloy is put into quartz glass tube, adopts induction melting remelting under argon shield, and makes mother alloy section bar by the casting of low pressure copper mold;
3rd step: by putting into the good crucible of pre-treatment after mother alloy section bar, under argon shield, adopts induction melting be heated to complete molten state and be incubated 10 minutes, implements rapid sequential subsequently and solidifies, form magnesium-base metal glass matrix material.
3. corrosion-resistant biological magnesium-base metal glass composite material and preparation method thereof according to claim 2, is characterized in that: the crucible that the first step and the 3rd step adopt is plumbago crucible, and its purity is higher than 99.9%; The purity of argon adopted in the first step, second step and the 3rd step is higher than 99.9%, and pressure is 0.06MPa; In 3rd step, the withdrawing rate of rapid sequential solidifying process controls at 3-10mm/s.
4. the corrosion-resistant biological magnesium-base metal glass matrix material according to claim 1-3, it is characterized in that: the overall dimension of magnesium-base metal glass matrix material reaches 16mm, first precipitated phase is long period Mg solid solution phase, its volume fraction can adjust arbitrarily within the scope of 30-80%, and is evenly distributed on magnesium-base metal glass matrix; The yield strength of described magnesium-base metal glass matrix material is greater than 700MPa, room temperature compression plasticity >=8%.
5. the corrosion-resistant biological magnesium-base metal glass matrix material according to claim 1-3, is characterized in that: the electrochemical corrosion potential E of magnesium-base metal glass matrix material in simulated body fluid
p>=-1.2V.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110042327A (en) * | 2019-05-28 | 2019-07-23 | 北方民族大学 | A kind of a wide range of controllable Biological magnesium alloy of degradation rate |
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|---|---|---|---|---|
| CN1403617A (en) * | 2001-09-13 | 2003-03-19 | 中国科学院金属研究所 | Multicomponent magnesium-base amorphous alloy containing zinc element |
| KR20060130324A (en) * | 2005-06-14 | 2006-12-19 | 학교법인연세대학교 | Magnesium based metallic glasses with enhanced ductility |
| JP2007092103A (en) * | 2005-09-27 | 2007-04-12 | Japan Science & Technology Agency | Magnesium-based metallic glass alloy-metal granular composite material having ductility |
| CN102181809A (en) * | 2011-04-21 | 2011-09-14 | 南京理工大学 | Large-size metallic glass composite material with tensile ductility and preparation method thereof |
| CN103938125A (en) * | 2014-03-27 | 2014-07-23 | 同济大学 | Degradable biological magnesium-based amorphous alloy and preparation method thereof |
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2014
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1403617A (en) * | 2001-09-13 | 2003-03-19 | 中国科学院金属研究所 | Multicomponent magnesium-base amorphous alloy containing zinc element |
| KR20060130324A (en) * | 2005-06-14 | 2006-12-19 | 학교법인연세대학교 | Magnesium based metallic glasses with enhanced ductility |
| JP2007092103A (en) * | 2005-09-27 | 2007-04-12 | Japan Science & Technology Agency | Magnesium-based metallic glass alloy-metal granular composite material having ductility |
| CN102181809A (en) * | 2011-04-21 | 2011-09-14 | 南京理工大学 | Large-size metallic glass composite material with tensile ductility and preparation method thereof |
| CN103938125A (en) * | 2014-03-27 | 2014-07-23 | 同济大学 | Degradable biological magnesium-based amorphous alloy and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110042327A (en) * | 2019-05-28 | 2019-07-23 | 北方民族大学 | A kind of a wide range of controllable Biological magnesium alloy of degradation rate |
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